1. Field of the Invention
The present invention relates to a positive resist composition for use in the production process of a semiconductor such as IC, in the production of a circuit substrate of liquid crystal, thermal head or the like, and in the lithography process of other photo-applications; and a pattern forming method using the composition. More specifically, the present invention relates to a positive resist composition for immersion exposure, which is suitable for exposure by an immersion-type projection exposure apparatus using a light source of emitting far ultraviolet light at a wavelength of 300 nm or less; and a pattern forming method using the composition.
2. Description of the Related Art
Along with the miniaturization of semiconductor devices, the trend is moving into shorter wavelength of the exposure light source and higher numerical aperture (high NA) of the projection lens. At present, an exposure machine with NA of 0.84 has been developed, where an ArF excimer laser having a wavelength of 193 nm is used as the light source. As commonly well known, these can be expressed by the following formulae:(Resolving power)=k1·(λ/NA)(Focal depth)=±k2)/NA2 wherein λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k1 and k2 are constants related to the process.
In order to realize still shorter wavelength and higher resolving power, studies are being made on an exposure machine where an F2 excimer laser having a wavelength of 157 nm is used as the light source. However, the lens material used for the exposure apparatus so as to realize shorter wavelength and the material used for the resist are very limited and therefore, it is extremely difficult to stabilize the production cost or quality of the apparatus and materials. This may lead to a failure in procuring the exposure apparatus and the resist each assured of sufficiently high performance and stability within a required time period.
Conventionally, a so-called immersion method of filling a high refractive-index liquid (hereinafter sometimes referred to as an “immersion liquid”) between the projection lens and the sample has been known as a technique of increasing the resolving power in an optical microscope.
As for the “effect of immersion”, assuming that the wavelength of exposure light in air is λ0, the refractive index of the immersion liquid to air is n, the convergence half-angle of beam is θ and NA0=sin θ, the above-described resolving power and focal depth when immersed can be expressed by the following formulae:(Resolving power)=k1(λ0/n)/NA0 (Focal depth)=±k2·(λ0/n)/NA02 
That is, the effect of immersion is equal to use of an exposure wavelength of 1/n. In other words, in the case of a projection optical system with the same NA, the focal depth can be made n times larger by the immersion. This is effective for all pattern profiles and can be combined with super-resolution techniques such as phase-shift method and modified illumination method which are being studied at present.
Examples of the apparatus where this effect is applied to the transfer of a fine image pattern of a semiconductor device are described in JP-A-57-153433 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”).
Recent progress of the immersion exposure technique is reported, for example, in SPIE Proc., 4688, 11 (2002), J. Vac. Sci. Tecnol. B, 17 (1999) and SPIE Proc., 3999, 2 (2000). In the case of using an ArF excimer laser as the light source, in view of safety on handling as well as transmittance and refractive index at 193 nm, pure water (refractive index at 193 nm: 1.44) is considered to be a most promising immersion liquid. In the case of using an F2 excimer laser as the light source, a fluorine-containing solution is being studied in the light of balance between transmittance and refractive index at 157 nm, but those satisfied in view of environmental safety or refractive index have been not yet found out. Considering the degree of immersion effect and the maturity of resist, the immersion exposure technique is expected to be most soon mounted on an ArF exposure machine.
Since the discovery of a resist for a KrF excimer laser (248 nm), an image forming method called chemical amplification is used as the image forming method for a resist so as to compensate the reduction in the sensitivity due to light absorption. The image forming method, for example, using positive chemical amplification is an image forming method where an acid generator in the exposed area decomposes upon exposure to generate an acid, the acid generated is used as a reaction catalyst in the baking after exposure (PEB: post exposure bake) to convert the alkali-insoluble group into an alkali-soluble group, and the exposed area is removed by an alkali developer.
A resist for an ArF excimer laser (wavelength: 193 nm) using this chemical amplification mechanism is predominating at present, and a resist composition ensuring the same performance even in the immersion exposure as that in the normal exposure (dry exposure) is demanded.
Also, it is pointed out that when the chemical amplification resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid at the exposure, as a result, the resist layer deteriorates or a component adversely affecting the immersion liquid bleeds out from the resist layer. International Publication No. WO 2004-068242, pamphlet describes a case where when the resist for ArF exposure is dipped in water before and after exposure, the resist performance is changed, and this is indicated as a problem in the immersion exposure.
Furthermore, in the immersion exposure process, when the exposure is performed by using a scanning-type immersion exposure machine, unless the immersion liquid moves following the movement of lens, the exposure speed decreases and this may affect the productivity. In the case where the immersion liquid is water, the resist film is preferably hydrophobic because of good followability of water.
On the other hand, studies are being made on a resist composition containing a fluorine atom or a silicon atom from the following various standpoints.
JP-A-2000-338676 discloses a resist composition comprising a specific resin and a fluorine-containing and/or silicon-containing surfactant, which ensures that in the image forming method by dry exposure, the sensitivity, resolving power, dry etching resistance and adhesion to substrate are excellent and the problems of development defect and scumming are overcome.
Japanese Patent No. 3,202,979 discloses a resist composition comprising a silicon-containing polymer additive and a silicon-free base polymer for enhancing the resolution and etching resistance.
Japanese Patent No. 3,672,780 discloses a resist composition comprising a (meth)acrylic acid ester unit with the ester moiety being a fluorine atom-containing group, which is a resist composition having high transparency and high sensitivity to VUV light and F2 excimer laser light.
As described above, a resist for an ArF excimer laser (wavelength: 193 nm) using the chemical amplification mechanism is predominating at present, but it is requested to more enhance the performance such as profile and defocus latitude (DOF). Also, a resist composition exhibiting the same performance even when subjected to immersion exposure is demanded. The defocus latitude is a tolerance for focus fluctuation at the exposure.